Two-dimensional metal-organic framework with wide channels and responsive turn-on fluorescence for the chemical sensing of volatile organic compounds.

We report a 2D layered metal-organic framework (MOF) with wide channels named NUS-1 and its activated analogue NUS-1a composed of Zn4O-like secondary building units and tetraphenylethene (TPE)-based ligand 4,4'-(2,2-diphenylethene-1,1-diyl)dibenzoic acid. Due to its special structure, NUS-1a exhibits unprecedented gas sorption behavior, glass-transition-like phase transition under cryogenic conditions, and responsive turn-on fluorescence to various volatile organic compounds. Our approach using angular ligand containing partially fixed TPE units paves a way toward highly porous MOFs with fluorescence turn-on response that will find wide applications in chemical sensing.

BSA-tetraphenylethene derivative conjugates with aggregation-induced emission properties: fluorescent probes for label-free and homogeneous detection of protease and α1-antitrypsin.

Herein, BSA-tetraphenylethene derivative conjugates with aggregation-induced emission (AIE) properties were constructed and used as fluorescent probes for label-free detection of protease and α1-antitrypsin. Conjugated AIE probes were formed based on the electrostatic induced assembly between an ammonium cation of quaternized tetraphenylethene salt and carboxyl anion groups of BSA. While water soluble quaternized tetraphenylethene salt showed very low fluorescence in its well-dispersed state, obvious enhancement in the fluorescence of the aggregated tetraphenylethene derivative on the BSA templates was achieved due to the abnormal aggregation-induced emission properties of tetraphenylethene. These BSA-tetraphenylethene derivative conjugates enabled label-free detection of protease. In the presence of trypsin, the BSA templates were enzymatically hydrolyzed and the conjugates decomposed. Therefore the quaternized tetraphenylethene molecules became increasingly isolated from each other. Accordingly, the aggregation to dispersing state change of tetraphenylethene derivative resulted in an obvious decrease in the fluorescence of the conjugates probes and enabled the sensitive and selective detection of trypsin. Furthermore, upon addition of α1-antitrypsin, the enzymatic activity of trypsin was inhibited and the fluorescence was consequently preserved. Sensitive detection of α1-antitrypsin was thus realised. The protein-tetraphenylethene derivative conjugates with aggregation-induced emission properties therefore show great promise for the monitoring of biological processes and cancer diagnostics with simplicity, high sensitivity, and rapid response.

Highly soluble PEGylated pyrene-gold nanoparticles dyads for sensitive turn-on fluorescent detection of biothiols.

Highly soluble fluorescent pyrene derivative with substantially improved fluorescence intensity in aqueous buffer was obtained via PEGylation strategy. The highly soluble PEGylated pyrene (PEO-Py) non-covalently adsorbed onto the surface of gold nanoparticles (Au NPs) to form dyads with quenched fluorescence due to highly efficient energy transfer between PEO-Py and Au NPs. The PEO-Py/Au NPs dyads were used for the sensitive turn-on fluorescent detection of biothiols. The fluorescence of PEO-Py was restored by the addition of cysteine (Cys), indicating that Cys can modulate the energy transfer between PEO-Py and Au NPs. This phenomenon then allowed for the sensitive detection of Cys with a limit of detection (LOD) of 11.4 nM. The linear range of determination of Cys was from 1.25 x 10(-8) to 2.25 x 10(-7) M. None of the other amino acids found in proteins showed obvious interference with the determination. It was important to note that the detection sensitivity of the PEO-Py/Au NPs system was more than 5-fold improved compared with the Py/Au NPs system. In addition, other biothiol molecules, such as glutathione, could also be detected by this sensor system. The method was also successfully applied to the determination of the total content of aminothiols in human plasma. Therefore an easily prepared, inexpensive, high solubility fluorescent probe has been realized and is also expected to detect other biological analytes of interest.

Label-free fluorescence detection of mercury(II) and glutathione based on Hg2+-DNA complexes stimulating aggregation-induced emission of a tetraphenylethene derivative.

Herein, a sensitive and selective sensor for mercury(II) and glutathione based on the aggregation-induced emission (AIE) of a tetraphenylethene derivative stimulated by Hg(2+)-DNA complexes is reported. Aggregation complexes of AIE probes, quaternized tetraphenylethene salt and anti-Hg(2+) aptamer ssDNA, were formed based on the electrostatic interactions between the ammonium cation of AIE probes and the backbone phosphate anions of DNA. In the presence of target Hg(2+), the aptamer ssDNA with thymine (T)-rich sequences selectively bound with Hg(2+) to form an Hg(2+)-bridged T base pair and the ssDNA changed into a hairpin-like structure. Therefore the AIE probing molecules were brought to be positioned closer. Accordingly, the conformational change of aptamer ssDNA resulted in an obvious enhancement in the fluorescence of the probing complex enabling the sensitive and selective detection of Hg(2+). Furthermore, upon reaction of Hg(2+) with biothiols, the compact structure was destroyed and the fluorescence decreased consequently. Sensitive detection of GSH was realised based on the decrease of fluorescence of the probing complex. The target-aptamer complexes stimulating aggregation-induced emission therefore show great promise for environmental and biological process monitoring and disease diagnosis.

Uptake, Distribution, and Bioimaging Applications of Aggregation-Induced Emission Saponin Nanoparticles in Arabidopsis thaliana.

The application of aggregation-induced emission luminogens (AIEgens) has heralded a new age in the analysis of subcellular events and has overcome many of the limitations of conventional fluorescent probes. Despite the extensive literature investigating AIEgens in mammalian cells, few reports exist of their bioimaging applications in plant cells. In this report, we describe the first systematic investigation of the uptake, distribution, and bioimaging applications of AIEgens and AIE saponin nanoparticles in the plant model system Arabidopsis thaliana. We find that the superior photostability, high colocalization with fluorescent proteins, and unique tissue-specific turn-on emission properties make AIEgens well-suited to tackle the emergent challenges faced in plant bioimaging.

AIEgen-based theranostic system: targeted imaging of cancer cells and adjuvant amplification of antitumor efficacy of paclitaxel.

Photosensitizers are generally treated as key components for photodynamic therapy. In contrast, we herein report an aggregation-induced emission luminogen (AIEgen)-based photosensitizer (TPE-Py-FFGYSA) that can serve as a non-toxic adjuvant to amplify the antitumor efficacy of paclitaxel, a well-known anticancer drug, with a synergistic effect of "0 + 1 > 1". Besides the adjuvant function, TPE-Py-FFGYSA can selectively light up EphA2 protein clusters overexpressed in cancer cells in a fluorescence turn-on mode, by taking advantage of the specific YSA peptide (YSAYPDSVPMMS)-EphA2 protein interaction. The simple incorporation of FFG as a self-assembly-aided unit between AIEgen (TPE-Py) and YSA significantly enhances the fluorescent signal output of TPE-Py when imaging EphA2 clusters in live cancer cells. Cytotoxicity and western blot studies reveal that the reactive oxygen species (ROS) generated by TPE-Py-FFGYSA upon exposure to light do not kill cancer cells, but instead provide an intracellular oxidative environment to help paclitaxel have much better efficacy. This study thus not only extends the application scope of photosensitizers, but also offers a unique theranostic system with the combination of diagnostic imaging and adjuvant antitumor therapy.

A thiol probe for measuring unfolded protein load and proteostasis in cells.

When proteostasis becomes unbalanced, unfolded proteins can accumulate and aggregate. Here we report that the dye, tetraphenylethene maleimide (TPE-MI) can be used to measure cellular unfolded protein load. TPE-MI fluorescence is activated upon labelling free cysteine thiols, normally buried in the core of globular proteins that are exposed upon unfolding. Crucially TPE-MI does not become fluorescent when conjugated to soluble glutathione. We find that TPE-MI fluorescence is enhanced upon reaction with cellular proteomes under conditions promoting accumulation of unfolded proteins. TPE-MI reactivity can be used to track which proteins expose more cysteine residues under stress through proteomic analysis. We show that TPE-MI can report imbalances in proteostasis in induced pluripotent stem cell models of Huntington disease, as well as cells transfected with mutant Huntington exon 1 before the formation of visible aggregates. TPE-MI also detects protein damage following dihydroartemisinin treatment of the malaria parasites Plasmodium falciparum. TPE-MI therefore holds promise as a tool to probe proteostasis mechanisms in disease.Proteostasis is maintained through a number of molecular mechanisms, some of which function to protect the folded state of proteins. Here the authors demonstrate the use of TPE-MI in a fluorigenic dye assay for the quantitation of unfolded proteins that can be used to assess proteostasis on a cellular or proteome scale.

Activatable Fluorescent Nanoprobe with Aggregation-Induced Emission Characteristics for Selective In Vivo Imaging of Elevated Peroxynitrite Generation.

An activatable fluorescent nanoprobe with aggregation-induced emission signature is developed. The nanoprobe is nonfluorescent, but can be induced to emit intensely after reaction with peroxynitrite forming an intramolecular hydrogen bond. Excellent performance for selective in vivo imaging of inflammation with elevated peroxynitrite generation and efficient visualization of in vivo treatment efficacy of anti-inflammatory agents is demonstrated.

An AIE-active fluorescence turn-on bioprobe mediated by hydrogen-bonding interaction for highly sensitive detection of hydrogen peroxide and glucose.

An AIE-active "turn-on" bioprobe is designed for hydrogen peroxide detection based on an imine-functionalized tetraphenylethene derivative. The linear fluorescence response enables quantification of hydrogen peroxide with superior sensitivity and selectivity. Meanwhile, glucose assay is also realized by taking advantage of GOx/glucose enzymatic reaction.

AEE-active cyclic tetraphenylsilole derivatives with ∼100% solid-state fluorescence quantum efficiency.

Two new strongly AEE active (I/I0 ≈ 94) tetraphenylsilole-containing cyclosiloxanes with cyan emissions (λem = 500 nm) and ∼100% solid state fluorescence quantum yields are reported. The intra- and intermolecular C-Hπ interactions in the crystal play a major role in the observed high solid state fluorescence quantum yields.

Effect of ionic interaction on the mechanochromic properties of pyridinium modified tetraphenylethene.

A pyridinium modified tetraphenylethene-based salt shows aggregation-induced emission enhancement properties and irreversible mechanochromic behaviours.

A ratiometric fluorescent probe based on ESIPT and AIE processes for alkaline phosphatase activity assay and visualization in living cells.

Alkaline phosphatase (ALP) activity is regarded as an important biomarker in medical diagnosis. A ratiometric fluorescent probe is developed based on a phosphorylated chalcone derivative for ALP activity assay and visualization in living cells. The probe is soluble in water and emits greenish-yellow in aqueous buffers. In the presence of ALP, the emission of probe changes to deep red gradually with ratiometric fluorescent response due to formation and aggregation of enzymatic product, whose fluorescence involves both excited-state intramolecular proton transfer and aggregation-induced emission processes. The linear ratiometric fluorescent response enables in vitro quantification of ALP activity in a range of 0-150 mU/mL with a detection limit of 0.15 mU/mL. The probe also shows excellent biocompatibility, which enables it to apply in ALP mapping in living cells.

A dual-mode fluorescence "turn-on" biosensor based on an aggregation-induced emission luminogen.

A novel dual-mode fluorescence "turn-on" probe is developed based on a phosphorylated tetraphenylethene (TPE) derivative bearing aggregation-induced emission (AIE) characteristics. The probe is weakly emissive in aqueous solution but its fluorescence is significantly enhanced in the presence of protamine or alkaline phosphatase (ALP). The cationic protamine interacted with the anionic phosphate group of the amphiphilic probe via electrostatic interaction and induced micelle formation. This micelle aggregates the hydrophobic TPE core and results in fluorescence enhancement. The detection limit for the protamine assay reached as low as 12 ng mL-1. On the other hand, ALP hydrolysed the fluorescent probe and led to self-aggregation of insoluble fluorescent residues. The linear light-up response of the probe enables ALP quantification in the range of 10-200 mU mL-1, which covers the physiological level of ALP activity in human serum. Moreover, the two activation modes could be differentiated by distinct responses to protamine and ALP.

Fluorescence detection of alkaline phosphatase activity with ß-cyclodextrin-modified quantum dots.

An alkaline phosphatase activity detection system was constructed based on the different quenching effect of the enzyme substrate and product on the ß-CD-functionalized CdTe QDs.